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November 2007
Rationale
This presentation provides common examples of recurring questions students pose in developing their proficiency in electrochemistry & corrosion. Typically these questions recur every year, year after year. The vast majority of such questions relate to critical basic information covered in the first few weeks, i.e. the foundation upon which the rest of the course depends. Computer software is a practical way to expose students to these questions.
Recurring Questions
Most recurring questions asked fall into one of the following areas:
Terminology (knowing new terms, e.g. cathode vs. anode) Thermodynamics (e.g. using the Nernst equation) Sign conventions (e.g. G = +nFE vs. G = nFE) Reference electrodes Understanding the significance of the cathodic reaction Understanding corrosion potentials
Electrochemistry (corrosion) is loaded with interrelated terms somewhat unique to the discipline, for example: Anode Anodic Active Oxidation Oxidation potential EMF series Electrolytic cell Cathode Cathodic Noble Reduction Reduction potential Galvanic series Galvanic cell
Terms on left & right are related, but are NOT equal. It is best to clearly define all of these from day one!
On the first day of class students are provided a handout entitled Important Corrosion Concepts to Remember defining most of these terms. That handout is available here: http://bama.ua.edu/~gwarren/ The explanation of electrolytic cells vs. galvanic cells is best covered after some exposure to the EMF series and Nernst equation (also found at the end of this presentation).
What are the most important things to know about the EMF Series?
Emphasize the title Standard Reduction Potentials, E or Standard Oxidation Potentials, E Each potential is tied to a half cell reaction. Electrochemical reactions (corrosion) must involve two half cells: one oxidation and one reduction. The half cell assigned a voltage of zero is the reference half cell. Always include V vs. SHE or V vs. SCE (only then is choice of reference half cell clear).
The connection between Gibbs energy (G) and potential or voltage (V) is given by either: G = nFE OR G = +nFE The choice is a convention, either is correct. Persistent repetition of the texts choice of nFE or +nFE is worthwhile for two reasons: To emphasize that this is the texts convention To emphasize the importance of identifying the chosen convention when consulting other texts or references I prefer using G = nFE, until students have some experience with the EMF series & the Nernst equation.
Imagine three EMF series (no others are possible!). The words oxidation or reduction with respect to cell potentials also indicates selection of nFE convention.
Standard Reduction Potentials (G = nFE) E (V) Cu2+ +2e = Cu + 0.342 2H+ + 2e = H2 0.0 Ni2+ +2e = Ni 0.250 Standard Potentials (G = +nFE) E (V) Cu2+/Cu + 0.342 H+/ H2 0.0 Ni2+/Ni - 0.250
Standard Oxidation Potentials (G = nFE) E (V) Cu = Cu2+ +2e 0.342 H2 = 2H+ + 2e 0.0 Ni = Ni2+ +2e + 0.250
Sign of E does NOT change if reactions are reversed, hence the title omits oxidation or reduction
Standard Oxidation Potentials (G = nFE) E (V) Cu = Cu2+ +2e 0.342 H2 = 2H+ + 2e 0.0 Ni = Ni2+ +2e + 0.250
For +nFE, sign of E is the experimentally observed value of selected cell when connected with H+/H2 half cell, so only one value is ever observed.
Ecorr Software
Computer Aided Instruction (CAI) is a practical way to expose students to recurring questions.
Permits students to work outside class at any time Allows more class time for other topics
Ecorr software
An introduction to corrosion, electrode potentials & electrochemical thermodynamics. Focuses on many recurring corrosion questions via examples and practice problems.
The following screens give a number of examples. Some previous exposure to thermodynamics is useful The user interacts with the program in various ways:
Answers to questions or calculations are entered by typing in boxes or by clicking buttons Clicking on red hot text opens popup windows with more information on that term, concept or calculation. Standard potentials are available in a pull down menu Menu allows user to navigate to other parts of program Any screen can be printed.
There are several other examples similar to the one shown here.
Whats the difference between a half cell potential and a corrosion potential?
The diagram shows that a corrosion potential is a combination of two half cells, the oxidation of Fe and the reduction of O2?
Red numbers reveal popup windows that show how the value was calculated.
Whats the difference between the Galvanic Series & EMF Series?
After giving a definition of each series, the user measures the corrosion potential for each metal by clicking & dragging each one into the white box. This shows that Ecorrs are not single half cells.
Shown is one example, for Fe and brass. User must enter answers to questions in boxes.
Examples: AA battery, car battery (when it is being discharged), i.e. nearly every corrosion reaction
Examples: electroplating of Cu, Au, Ag, car battery (when it is being charged)
Galvanic Cell e-
Electrolytic Cell
(electrolysis of water)
e-
+
O2
PS
H2
Zn
Cu
Zn+2 soln
ANODE
Cu+2 soln
CATHODE
Pt
Pt
ANODE
CATHODE
Zn = Zn+2+2eoxidation
Cu+2+2e- = Cu reduction
2H2O = O2+2H++2eoxidation
2H++2e- = H2 reduction
Remember
Corrosion is inevitable. Only under impractical conditions can it be 100% eliminated, but we can reduce or minimize it. Ecorr program downloads are available through MaterialsTechnology@TMS http://materialstechnology.tms.org/educ/educdigital.asp Contact information:
Comments are welcome, please reply via MaterialsTechnology@TMS